Catalyst for hydrogenation reaction and method for producing same

ABSTRACT

A catalyst for a hydrogenation reaction including: a polymer support; and a catalytic component supported on the polymer support. The polymer support includes a repeating unit represented by Formula 1.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a U.S. national stage of international ApplicationNo. PCT/KR2020/009186 filed on Jul. 13, 2020, and claims priority to andthe benefit of Korean Patent Application No. 10-2019-0120804 filed inthe Korean Intellectual Property Office on Sep. 30, 2019, the entirecontents of which are incorporated herein by reference.

TECHNICAL FIELD

The present invention relates to a catalyst for a hydrogenation reactionand a method for manufacturing the same.

BACKGROUND

Oil refinery and petrochemical plants produce large amounts ofhydrocarbons, which contain large amounts of unsaturated hydrocarbonswhich cause problems during subsequent process steps or storage periods.Examples of these unsaturated hydrocarbons include acetylene, propyne,propadiene, butadiene, vinylacetylene, butyne, phenylacetylene, styreneand the like.

As an example, acetylene is known to reduce the activity of a catalystin an ethylene polymerization process and cause a deterioration in thequality of a polymer. Therefore, in a process of synthesizingpolyethylene from ethylene, the concentration of acetylene contained inethylene raw materials needs to be reduced to a minimal level.

These undesirable unsaturated compounds are usually removed to severalPPM or less by a selective hydrogenation reaction. It is very importantto enhance the selectivity of a desired compound from a reaction ofselectively hydrogenating unsaturated compounds to avoid coke formation,which reduces the reaction activity.

In related art, nickel sulfate, tungsten/nickel sulfate or coppercontaining catalysts have been used for selective hydrogenationreactions. However, these catalysts have low catalytic activity even athigh temperatures, and thus reduce polymer formation. Further, supportedpalladium (Pd) or Pd and silver (Ag) containing catalysts based onalumina or silica are also used in selective hydrogenation processes,but the selectivity is unsatisfactory or the activity is low.

Therefore, there is a need in the art for developing a catalyst for ahydrogenation reaction, which has excellent selectivity for a product ofhydrogenation reaction and excellent catalytic activity.

SUMMARY

The present application provides a catalyst for a hydrogenation reactionand a method for manufacturing the same.

An exemplary embodiment of the present application provides a catalystfor a hydrogenation reaction, the catalyst comprising:

a polymer support; and

a catalytic component supported on the polymer support,

wherein the polymer support comprises a repeating unit represented bythe following Formula 1:

In Formula 1:

L1 and L3 are the same as or different from each other, and are eachindependently 0 or NH,

L2 is O, NH, or S,

R1 and R2 are the same as or different from each other, and are eachindependently hydrogen, an alkyl group having 1 to 10 carbon atoms, oran aryl group having 6 to 20 carbon atoms,

m is 0 or 1, and

p and q are each independently an integer from 0 to 4.

Further, another exemplary embodiment of the present applicationprovides a method for manufacturing a catalyst for a hydrogenationreaction, the method comprising:

preparing a polymer support comprising the repeating unit represented byFormula 1; and

supporting a catalytic component on the polymer support.

According to an exemplary embodiment of the present application, apolymer support comprising the repeating unit represented by Formula 1can be applied as a support for a catalyst for a hydrogenation reaction.

Further, according to an exemplary embodiment of the presentapplication, the catalyst comprising the polymer support has excellentstability when used at a temperature in the reaction temperature rangeof a hydrogenation reaction and improves the selectivity for the productof the hydrogenation reaction.

In addition, a catalyst for a hydrogenation reaction according to anexemplary embodiment of the present application has reactioncharacteristics which are different from those of an alumina- orsilica-based metal-supported catalyst described in related art. In anexemplary embodiment of the present application, the reaction occurs onthe surface of the metal due to a strong bond between a polymer supportcomprising the repeating unit represented by Formula 1 and a hydrogenactive metal cluster. The catalyst for a hydrogenation reactionaccording to an exemplary embodiment of the present application hasexcellent stability within a reaction temperature range of thehydrogenation reaction and improves the selectivity of alkene in thehydrogenation reaction of alkyne by suppressing the hydrogenationreactivity of alkene while maintaining the hydrogenation reactivity ofalkyne.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1A, 1B, 2A and 2B are ¹³C nuclear magnetic resonance (NMR)analysis results of polymer supports prepared according to SynthesisExamples 1 to 4, respectively.

FIGS. 3A, 3B, 4A and 4B are differential scanning calorimetry (DSC)analysis results of the polymer supports prepared according to SynthesisExamples 1 to 4, respectively.

FIG. 5 is a graphical representation of the thermal gravimetric analysis(TGA) results of catalysts according to Examples 1 to 4, respectively,in a H₂ atmosphere.

FIGS. 6A, 6B, 7A and 7B are TEM images of the catalysts according toExamples 1 to 4, respectively.

FIGS. 8A, 8B, 9A and 9B are acetylene hydrogenation reaction results ofthe catalysts according to Examples 1 to 4, respectively, showing theconversion or selectivity as relates to the value of 1/WHSV.

FIG. 10 is a schematic illustration of a method for supporting acatalytic component on a polymer support according to an exemplaryembodiment of the present application.

FIG. 11 is a graphical representation of the thermal gravimetricanalysis (TGA) results of catalysts according to Examples 5 to 9,respectively, in a H₂ atmosphere.

DETAILED DESCRIPTION

Hereinafter, the present specification will be described in more detail.

When one member is disposed “on” another member in the presentspecification, this includes not only a case where the one member isbrought into contact with another member, but also a case where stillanother member is present between the two members.

When one part “comprises” one constituent element in the presentspecification, unless otherwise specifically described, this does notmean that another constituent element is excluded, but means thatanother constituent element can be further included.

As described above, it is common to use a catalyst in which Pd issupported on an alumina support as a catalyst for a hydrogenationreaction, as described in related art. However, such related artcatalysts have a problem in that the catalyst replacement cycle is shortdue to the rapid deactivation of the catalyst, and thus process costsare increased. Further, to improve the selectivity of the product ofhydrogenation reaction in the related art, a modifier was introduced,but the introduction of the modifier has a problem in that the processcost increases and an additional separation process is required.

Thus, the present application was intended to develop a catalyst for ahydrogenation reaction, which has excellent selectivity for the productof a hydrogenation reaction and excellent catalytic activity. Inparticular, the present inventors have developed a catalyst comprising apolymer support applied to a catalyst for a hydrogenation reaction.

The catalyst for a hydrogenation reaction according to an exemplaryembodiment of the present application comprises: a polymer support; anda catalytic component supported on the polymer support, in which thepolymer support comprises a repeating unit represented by the followingFormula 1:

In Formula 1:

L1 and L3 are the same as or different from each other, and are eachindependently 0 or NH,

L2 is O, NH, or S,

R1 and R2 are the same as or different from each other, and are eachindependently hydrogen, an alkyl group having 1 to 10 carbon atoms, oran aryl group having 6 to 20 carbon atoms,

m is 0 or 1, and

p and q are each independently an integer from 0 to 4.

In an exemplary embodiment of the present application, “

” in the formulae means a point where the repeating units are linked.

In an exemplary embodiment of the present application, the alkyl groupof Formula 1 can be straight-chained or branched, and the number ofcarbon atoms thereof is not particularly limited, but is preferably 1 to10. Specific examples of the alkyl group include a methyl group, anethyl group, a propyl group, an isopropyl group, a butyl group, ann-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group,a 1-methylbutyl group, a 1-ethylbutyl group, and the like, but are notlimited thereto.

In an exemplary embodiment of the present application, specific examplesof the aryl groups of Formula 1 can include a phenyl group, a biphenylgroup, a terphenyl group, a quaterphenyl group, a naphthyl group, ananthracenyl group, a phenanthrenyl group, a pyrenyl group, and the like,but are not limited thereto.

In an exemplary embodiment of the present application, both R1 and R2 ofFormula 1 can be hydrogen.

In an exemplary embodiment of the present application, L1 and L3 can bethe same as each other.

In an exemplary embodiment of the present application, Formula 1 can berepresented by any one of the following Formulae 2 to 12:

In an exemplary embodiment of the present application, the polymersupport has a structure in which a triazine ring and a benzene ring arelinked to each other by intermediate linking groups (L1 and L3). Thatis, three -L1 functional groups bonded to the triazine ring of Formula 1are each bonded to a benzene ring, and one -L3 functional group bondedto the benzene ring has a structure in which the -L3 functional group isbonded to the triazine ring.

In an exemplary embodiment of the present application, the polymersupport is composed of a cross-linked polymer, so that the molecularweight of the cross-linked polymer is not specified.

According to an exemplary embodiment of the present application, it ispossible to exhibit high selectivity compared to a hydrogenationcatalyst using a related art alumina or silica support in a selectivehydrogenation reaction such as hydrogenation of alkyne to alkene bysupporting a hydrogen active metal (a metal capable of forming hydrogenactivated by contact with hydrogen molecules) in the polymer support. Asan example, in the hydrogenation reaction of alkyne to alkene, in thecase of a related art alumina- or silica-based metal supported catalyst,both alkyne and alkene are easily adsorbed on the surface of the metal,so that hydrogenation of alkyne to alkene and hydrogenation of alkene toalkane are non-selectively accomplished. However, as in an exemplaryembodiment of the present application, when the polymer support is used,the surface of an active metal is surrounded by the polymer due to thestrong binding power between the polymer support and the active metal.Therefore, based on the active metal, a reactant exhibiting a relativelystronger binding power than the binding power between the active metaland the polymer support, such as an alkyne, is adsorbed on the activemetal, but reactants exhibiting a relatively weaker binding power, suchas alkene, cannot be adsorbed on the active metal. Due to thesecharacteristics, a catalyst having an active metal supported on apolymer support can show high selectivity in a hydrogenation reaction ofalkyne to alkene by suppressing the hydrogenation reactivity of alkenewhile maintaining the hydrogenation reactivity of alkyne.

In an exemplary embodiment of the present application, the catalyticcomponent can include one or more of platinum (Pt), palladium (Pd),ruthenium (Ru), iron (Fe), nickel (Ni), cobalt (Co), molybdenum (Mo),gold (Au), silver (Ag), copper (Cu), titanium (Ti), gallium (Ga), cerium(Ce), aluminum (Al), zinc (Zn), and lanthanum (La).

In an exemplary embodiment of the present application, a content of thecatalytic component can be 0.01 wt % to 10 wt % and 0.05 wt % to 5 wt %,based on a total weight of the catalyst for a hydrogenation reaction.When the content of the catalytic component is less than 0.01 wt % basedon the total weight of the catalyst for a hydrogenation reaction, thereactivity of the catalyst can deteriorate. Further, when the content ofthe catalyst component is more than 10 wt %, a relatively large amountof active metal is contained compared to the polymer support, so thatthe active metal cannot be easily bonded to the polymer support, andaccordingly, the selectivity of alkene is lowered by hydrogenationreaction, so that the actual benefit of the hydrogenation reactioncaused by the increase in weight can be decreased.

A method for manufacturing a catalyst for a hydrogenation reactionaccording to an exemplary embodiment of the present applicationcomprises: preparing a polymer support comprising the repeating unitrepresented by Formula 1; and supporting a catalytic component on thepolymer support.

In an exemplary embodiment of the present application, the polymersupport comprising the repeating unit represented by Formula 1 can besynthesized by condensation polymerization of a monomer A comprising atriazine structure, a monomer B comprising a benzene ring, and a basicmaterial in a benzene ring. As an example, the monomer A can be acompound containing a cyanuric chloride or a triazine ring and having afunctional group capable of nucleophilic aromatic substitution. Further,examples of the monomer B include 4,4′-thiodiphenol, hydroquinone,4,4′-dihydroxydiphenyl ether, 1,4-phenylenediamine, and the like, butare not limited thereto.

In addition, when the polymer support is produced, a basic material canbe used in order to remove an acid which can be produced as a result ofa condensation polymerization reaction of the monomers A and B, and asthe basic material, N,N-diisopropylethylamine (DIPEA), K₂CO₃, and thelike can be used, but the basic material is not limited thereto.Furthermore, examples of the solvent which can be used in thecondensation polymerization reaction of the monomers A and B include anaprotic solvent such as 1,4-dioxane, acetonitrile, and cyclohexane, butare not limited thereto.

Further, a molar ratio of the monomer A/the monomer B can be 0.5 to 2,and it is possible to include an amount of basic material, which cansufficiently titrate an acid which is produced. For example, the amountof the basic material can be 3 equivalents or more of the molarequivalent of the monomer A.

In an exemplary embodiment of the present application, a method formanufacturing the polymer support reacts a monomer A, a monomer B, anorganic solvent, and a basic material while stirring the materials at 0°C. to 15° C. for 0.5 hour to 1 hour, 25° C. to 30° C. for 2 hours to 4hours, and 80° C. to 140° C. for 12 hours to 24 hours. Thereafter, thepolymer support can be produced by filtering a produced polymer, washingthe filtered polymer with a solvent such as methanol, ethanol, andacetone, and then drying the polymer at 60° C. to 100° C.

In an exemplary embodiment of the present application, in the method forsupporting a catalytic component on a polymer support, after an aqueoussolution or organic solution (supporting solution) containing a compoundas a precursor for the catalytic component is prepared, a catalyst canbe synthesized by using an immersion method in which the polymer supportis immersed in the supporting solution, dried, and then reduced withhydrogen gas to support the catalytic component, or by stirring theresulting polymer support with metal nanoparticles reduced in advance.As a precursor for the catalytic component, an organic metal compoundsuch as Pd(acac)₂, Pd(NO₃)₂.4NH₃, Pt(acac)₂, and Pt(NO₃)₂. 4NH₃ can beused, but the precursor is not limited thereto.

When the catalytic component is supported on the polymer support by theimmersion method, an aqueous solution or organic solution is prepared bydissolving a precursor of the catalytic component in water or an organicsolvent in a volume corresponding to voids of the polymer support,immersing a polymer support in the solution, completely evaporating thesolvent, and drying the resulting, and then the polymer can be reducedwhile flowing hydrogen within a temperature at which the polymer is notimpaired (<250° C.). Further, after metal nanoparticles reduced inadvance are dispersed in an organic solvent, a polymer support isimmersed in the solution, the solution is stirred and subjected toultrasonic treatment. A catalyst can be obtained by filtering theresulting solution until the color of the solution completely fades, andthen drying the filtered product.

As an exemplary embodiment of the present application, a method forsupporting a catalytic component on a polymer support is schematicallyillustrated in FIG. 10.

In a method for manufacturing a catalyst for a hydrogenation reactionaccording to an exemplary embodiment of the present application, detailsof the polymer support comprising the repeating unit represented byFormula 1, the catalytic component, and the like are the same as thosedescribed above.

The catalyst according to an exemplary embodiment of the presentapplication can be applied to a hydrogenation reaction. For example, thecatalyst can be applied to a hydrogenation reaction of alkene fromalkyne. The catalyst according to an exemplary embodiment of the presentapplication can be applied not only to acetylene, but also to ahydrocarbon compound having a triple bond. Examples of the hydrocarboncompound include propyne, butyne, pentyne, hexyne, heptyne, octyne, andthe like. Furthermore, in a compound comprising a functional group otherthan the triple bond or a double bond, for example, a compound having abenzene ring such as phenylacetylene, an alkyne compound having acarbonyl group, an alkyne compound having a carbonyl group, an alkynecompound having an alcohol group, an alkyne compound having an aminegroup, and the like, a hydrogenolysis reaction is suppressed, and onlyan alkyne group can be applied to a selective hydrogenation reaction toan alkene group.

Hereinafter, the present application will be described in detail withreference to Examples for specifically describing the presentapplication. However, the Examples according to the present applicationcan be modified in various forms, and it is not interpreted that thescope of the present application is limited to the Examples described indetail below. The Examples of the present application are provided formore completely explaining the present application to the person withordinary skill in the art.

EXAMPLES <Synthesis Example 1> Synthesis of Polymer Comprising RepeatingUnit Represented by Formula 2

A polymer comprising a repeating unit represented by Formula 2 wasproduced by polymerizing 4.79 g of cyanuric chloride (Sigma Aldrich) and8.52 g of 4,4′-thiodiphenol (Sigma Aldrich) with 260 ml of acetonitrileto which 10.78 g of a basic material K₂CO₃ (Alfa Aesar) was added in asolvent at 15° C. for 1 hour, 25° C. for 2 hours, and 90° C. for 72hours. The produced polymer is represented by Polymer 2.

<Synthesis Example 2> Synthesis of Polymer Comprising Repeating UnitRepresented by Formula 3

A polymer comprising a repeating unit represented by Formula 3 wasproduced in the same manner as in Synthesis Example 1, except that 4.29g of hydroquinone (Sigma Aldrich) was used instead of the4,4′-thiodiphenol. The produced polymer is represented by Polymer 3.

<Synthesis Example 3> Synthesis of Polymer Comprising Repeating UnitRepresented by Formula 4

A polymer comprising a repeating unit represented by Formula 4 wasproduced in the same manner as in Synthesis Example 1, except that 7.89g of 4,4′-dihydroxydiphenyl ether (Sigma Aldrich) was used instead ofthe 4,4′-thiodiphenol. The produced polymer is represented by Polymer 4.

<Synthesis Example 4> Synthesis of Polymer Comprising Repeating UnitRepresented by Formula 5

A polymer comprising a repeating unit represented by Formula 5 wasproduced in the same manner as in Synthesis Example 1, except that 4.22g of 1,4-phenylenediamine (Sigma Aldrich) was used instead of the4,4′-thiodiphenol. The produced polymer is represented by Polymer 5.

<Synthesis Example 5> Synthesis of Polymer Comprising Repeating UnitRepresented by Formula 6

A polymer comprising a repeating unit represented by Formula 6 wasproduced in the same manner as in Synthesis Example 1, except that 5.94g of trimethylhydroquinone was used instead of the 4,4′-thiodiphenol.

<Synthesis Example 6> Synthesis of Polymer Comprising Repeating UnitRepresented by Formula 7

A polymer comprising a repeating unit represented by Formula 7 wasproduced in the same manner as in Synthesis Example 1, except that 6.41g of 2,3,5,6-tetramethyl-p-phenylenediamine was used instead of the4,4′-thiodiphenol.

<Synthesis Example 7> Synthesis of Polymer Comprising Repeating UnitRepresented by Formula 8

A polymer comprising a repeating unit represented by Formula 8 wasproduced in the same manner as in Synthesis Example 1, except that 8.60g of 2,5-diaminotoluene sulfate was used instead of the4,4′-thiodiphenol.

<Synthesis Example 8> Synthesis of Polymer Comprising Repeating UnitRepresented by Formula 9

A polymer comprising a repeating unit represented by Formula 9 wasproduced in the same manner as in Synthesis Example 1, except that 6.49g of tert-butylhydroquinone was used instead of the 4,4′-thiodiphenol.

<Synthesis Example 9> Synthesis of Polymer Comprising Repeating UnitRepresented by Formula 10

A polymer comprising a repeating unit represented by Formula 10 wasproduced in the same manner as in Synthesis Example 1, except that 7.27g of 2-phenylhydroquinone was used instead of the 4,4′-thiodiphenol.

<Experimental Example 1> Structure and Characteristic Analysis ofSynthesized Polymer Support

In order to confirm the structures of the polymer supports produced inSynthesis Examples 1 to 4, a ¹³C NMR analysis was performed, and thenthe results thereof are shown in the following FIGS. 1A, 1B, 2A and 2B,respectively. As shown by the data in FIGS. 1A, 1B, 2A and 2B, all thesynthesized polymer supports of Synthesis Examples 1 to 4 have the samestructure as the corresponding chemical formula.

For the analysis of the physical properties of the polymer supportsproduced in Synthesis Examples 1 to 4, a differential scanningcalorimetry (DSC) analysis was performed, and then the results thereofare shown in the following FIGS. 3A, 3B, 4A and 4B, respectively. Asshown by the results of FIGS. 3A, 3B, 4A and 4B, the synthesizedpolymers were present in a cross-linked state.

<Example 1> Manufacture of Polymer Support-Based Hydrogenation Catalyst

1) Synthesis of Palladium Cluster

15 ml of oleylamine and 75 mg of Pd(acac)₂ were mixed in an argonatmosphere and stirred at 60° C. for 1 hour. Thereafter, 300 mg of aborane tert-butylamine complex and 3 ml of an oleylamine mixture wereput into the aforementioned mixture, and the resulting mixture washeated at 90° C. and stirred for 1 hour. Thereafter, 30 ml of ethanolwas put into the mixture, and then a palladium cluster was obtainedthrough centrifugation, and the obtained palladium cluster was dispersedin 20 ml of hexane and stored as a palladium-hexane solution.

2) Supporting Palladium Cluster on Polymer Support

1 g of the polymer support produced in Synthesis Example 1 was put into50 ml of a hexane solution and stirred (a mixture A). 0.76 ml of thesynthesized palladium-hexane solution and 50 ml of a hexane solutionwere mixed (a mixture B). The mixture B was slowly dropped onto thestirring mixture A, and then the resulting mixture was stirred for 2hours. The stirred mixture was ultrasonicated for 2 hours, and thenfiltered, and dried at room temperature. The dried product was added to30 ml of acetic acid, and the resulting mixture was stirred at 40° C.for 12 hours, filtered, washed with 300 ml of ethanol, and then dried atroom temperature for 12 hours. The produced catalyst is represented by“Pd/Polymer 2”.

<Example 2> Manufacture of Polymer Support-Based Hydrogenation Catalyst

A process was performed in the same manner as in Example 1, except thatthe polymer support produced in Synthesis Example 2 was used instead ofthe polymer support produced in Synthesis Example 1. The producedpolymer is represented by “Pd/Polymer 3”.

<Example 3> Manufacture of Polymer Support-Based Hydrogenation Catalyst

A process was performed in the same manner as in Example 1, except thatthe polymer support produced in Synthesis Example 3 was used instead ofthe polymer support produced in Synthesis Example 1. The producedcatalyst is represented by “Pd/Polymer 4”.

<Example 4> Manufacture of Polymer Support-Based Hydrogenation Catalyst

A process was performed in the same manner as in Example 1, except thatthe polymer support produced in Synthesis Example 4 was used instead ofthe polymer support produced in Synthesis Example 1. The producedcatalyst is represented by “Pd/Polymer 5”.

<Example 5> Manufacture of Polymer Support-Based Hydrogenation Catalyst

A process was performed in the same manner as in Example 1, except thatthe polymer support produced in Synthesis Example 5 was used instead ofthe polymer support produced in Synthesis Example 1.

<Example 6> Manufacture of Polymer Support-Based Hydrogenation Catalyst

A process was performed in the same manner as in Example 1, except thatthe polymer support produced in Synthesis Example 6 was used instead ofthe polymer support produced in Synthesis Example 1.

<Example 7> Manufacture of Polymer Support-Based Hydrogenation Catalyst

A process was performed in the same manner as in Example 1, except thatthe polymer support produced in Synthesis Example 7 was used instead ofthe polymer support produced in Synthesis Example 1.

<Example 8> Manufacture of Polymer Support-Based Hydrogenation Catalyst

A process was performed in the same manner as in Example 1, except thatthe polymer support produced in Synthesis Example 8 was used instead ofthe polymer support produced in Synthesis Example 1.

<Example 9> Manufacture of Polymer Support-Based Hydrogenation Catalyst

A process was performed in the same manner as in Example 1, except thatthe polymer support produced in Synthesis Example 9 was used instead ofthe polymer support produced in Synthesis Example 1.

Comparative Example 1

A process was performed in the same manner as in Example 1, except thatin Example 1, a commercially available alumina (Strem, 27976400) wasused instead of the polymer support used in Synthesis Example 1. Theproduced catalyst is represented by “Pd/γ-Al₂O₃”.

<Experimental Example 2> Structure and Characteristic Analysis ofCatalyst Having Metal Supported on Polymer Support

For the analysis of the physical properties of the Pd/polymer catalystsproduced in Synthesis Examples 1 to 9, a H₂ thermal gravimetric analysis(TGA) was performed using a thermal gravimetric analyzer, and theresults thereof are shown in the following FIGS. 5 and 11. Morespecifically, the spectra in FIGS. 5 and 11 show the change in weight ofthe polymer supports as the reaction temperature increases in a hydrogenatmosphere. FIGS. 5 and 11 show that all the Pd/polymer catalystsproduced in Examples 1 to 9 were stable up to 200° C. in a hydrogenatmosphere.

Transmission electron microscope (TEM) analysis was performed on thePd/polymer catalysts produced in Examples 1 to 4, and the resultsthereof are shown in the following FIGS. 6A, 6B, 7A and 7B. The TEMimages show that palladium particles having a diameter of about 5 nmwere uniformly dispersed on the polymer support over all the Pd/polymercatalyst manufactured in Examples 1 to 4, respectively.

<Experimental Example 3> Selective Hydrogenation Reaction of AcetyleneUsing Supported Catalyst

An acetylene selective hydrogenation reaction was performed on thehydrogenation catalysts manufactured in the Examples, and the resultsthereof are shown in the following FIGS. 8 and 9.

A selective hydrogenation reaction of acetylene was performed underconditions of 1 atm, 100° C., and a weight hourly space velocity (WHSV)of 0.021 to 1.25 g_(C2H2) g_(cat) ⁻¹h⁻¹ by feeding 0.6 kPa of acetylene,49.3 kPa of ethylene, and 0.9 kPa of hydrogen- and nitrogen-based gases.

In order to analyze product components in the hydrogenation reaction,the product components were analyzed using gas chromatography. Theconversion of a reactant (acetylene) and the selectivity of products(ethylene, ethane, and the like) were calculated by the followingEquations 1 and 2:

Conversion(%)=(the number of moles of acetylene reacted)/(the number ofmoles of acetylene fed)×100  [Equation 1]

Selectivity(%)=(the number of moles of product produced)/(the number ofmoles of acetylene reacted)×100.  [Equation 2]

The measured reaction results are shown in the following Table 1.

Analysis devices and analysis conditions applied in the presentapplication are as follows.

1) Cross polarization magic-angle spinning ¹³C nuclear magneticresonance (CP/MAS ¹³C NMR)

Used equipment: Avance III HD (400 MHz) with wide bore 9.4 T magnet(Bruker)

Analysis method: Larmor frequency of 100.66 MHz, repetition delay timeof 3 seconds. Chemical shifts were reported in ppm relative totetramethyl silane (0 ppm).

2) Differential scanning calorimetry (DSC):

Used equipment: DSC131 evo (Setaram).

Analysis method: After a sample was placed on an alumina pan, theconversion was measured by regulating the temperature at a rate of 5K/min from 313 K to 593 K.

3) Transmission electron microscope (TEM):

Used equipment: JEM-2100F (JEOL) at 200 kV.

4) Thermal gravimetric analysis (TGA):

Used equipment: TGA N-1000 (Scinco).

Analysis method: the conversion was measured by increasing thetemperature at 5 K/min from 323 K to 1,025 K.

5) Gas chromatography (GC):

Used equipment: YL6500 (Youngin).

Analysis method: on-line GC, equipped with flame ionized detector (FID),GS-GasPro (Agilent) column was used.

TABLE 1 WHSV Acetylene Ethane Ethylene Others (C₄) Type of (g_(C2H2)Conversion Selectivity Selectivity Selectivity catalyst g_(cat) ⁻¹h⁻¹)(%) (%) (%) (%) Example 1 0.021 100 46.22 37.66 16.12 Example 2 0.02194.72 63.07 22.15 14.78 Example 3 0.021 93.05 65.8 18.98 15.22 Example 40.021 96.57 61.71 24.06 14.23 Example 5 0.021 93.34 67.13 22.51 15.54Example 6 0.021 98.05 67.22 24.29 14.83 Example 7 0.021 95.14 64.2723.68 15.70 Example 8 0.021 98.87 65.10 25.04 14.87 Example 9 0.02194.60 66.81 23.33 16.21 Comparative 0.021 100 68.03 16.67 15.30 Example1

As shown by the results in Table 1, the catalyst for a hydrogenationreaction according to an exemplary embodiment of the present applicationhas excellent ethylene selectivity and acetylene conversion, and theethylene selectivity is better than that of the catalyst (Pd/γ-Al₂O₃) inComparative Example 1 at the same hourly space velocity.

From the experimental results using the polymer support comprising therepeating unit represented by any one of Formulae 2 to 10, similareffects can be obtained even when a functional group such as anotheralkyl group and aryl group having a similar action principle isadditionally bonded to a repeating unit represented by Formula 1.

Therefore, according to an exemplary embodiment of the presentapplication, a polymer support comprising the repeating unit representedby Formula 1 can be applied as a support of a catalyst for ahydrogenation reaction.

Further, according to an exemplary embodiment of the presentapplication, the catalyst comprising the polymer support ischaracterized by having excellent stability in the reaction temperaturerange of the hydrogenation reaction and being able to improve theselectivity for the product of the hydrogenation reaction.

1. A catalyst for a hydrogenation reaction, the catalyst comprising: apolymer support; and a catalytic component supported on the polymersupport, wherein the polymer support comprises a repeating unitrepresented by Formula 1:

wherein in Formula 1, L1 and L3 are the same as or different from eachother, and are each independently 0 or NH, L2 is O, NH, or S, R1 and R2are the same as or different from each other, and are each independentlyhydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl grouphaving 6 to 20 carbon atoms, m is 0 or 1, and p and q are eachindependently an integer from 0 to
 4. 2. The catalyst of claim 1,wherein both R1 and R2 are hydrogen.
 3. The catalyst of claim 1, whereinFormula 1 is represented by any one of Formulae 2 to 12:


4. The catalyst of claim 1, wherein the catalytic component comprisesone or more of platinum, palladium, ruthenium, iron, nickel, cobalt,molybdenum, gold, silver, copper, titanium, gallium, cerium, aluminum,zinc, and lanthanum.
 5. The catalyst of claim 1, wherein an amount ofthe catalytic component is 0.01 wt % to 10 wt % based on a total weightof the catalyst for a hydrogenation reaction.
 6. The catalyst of claim1, wherein the catalyst for a hydrogenation reaction is a catalyst for ahydrogenation reaction of alkyne to alkene.
 7. A method formanufacturing a catalyst for a hydrogenation reaction, the methodcomprising: preparing a polymer support comprising a repeating unitrepresented by Formula 1; and supporting a catalytic component on thepolymer support:

wherein in Formula 1, L1 and L3 are the same as or different from eachother, and are each independently 0 or NH, L2 is O, NH, or S, R1 and R2are the same as or different from each other, and are each independentlyhydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl grouphaving 6 to 20 carbon atoms, m is 0 or 1, and p and q are eachindependently an integer from 0 to
 4. 8. The method of claim 7, whereinFormula 1 is represented by any one of Formulae 2 to 12:


9. The method of claim 7, wherein the catalytic component comprises oneor more of platinum, palladium, ruthenium, iron, nickel, cobalt,molybdenum, gold, silver, copper, titanium, gallium, cerium, aluminum,zinc, and lanthanum.
 10. The method of claim 7, wherein an amount of thecatalytic component is 0.01 wt % to 10 wt % based on a total weight ofthe catalyst for a hydrogenation reaction.